Processes for preparing aqueous polymer emulsions

ABSTRACT

This invention relates to processes for preparing aqueous polymer emulsions useful as thickening agents in aqueous compositions in which plating and/or grit formation is reduced in said processes. This invention also relates to methods for reducing plating and/or grit formation in processes for preparing aqueous polymer emulsions useful as thickening agents in aqueous compositions. This invention further relates to polymers which are soluble in, or swelled by, an aqueous alkaline medium to provide thickeners for use in aqueous coating compositions, especially latex paints.

RELATED APPLICATIONS

This application is a Division of prior U.S. application Ser. No.8/521,420 Aug. 30, 1995 U.S. Pat. No. 5,561,189 which is a divisional ofapplication Ser. No. 08/414,005 Mar. 17, 1995, U.S. Pat. No. 5,476,900which is a divisional of application Ser. No. 08/342,147 Nov. 18, 1994,U.S. Pat. No. 5,436,292 which is a divisional of application Ser. No.08/083,896 Jun. 28, 1993, U.S. Pat. No. 5,399,618.

The folowing is a related, commonly assigned application, filed on aneven date herewith:

U.S. patent application Ser. No. 08/083,896 U.S. Pat. No. 5,399,618;which is incorporated herein by reference.

BRIEF SUMMARY OF THE INVENTION

1. Technical Field

This invention relates to processes for preparing aqueous polymeremulsions useful as thickening agents in aqueous compositions in whichplating and/or grit formation is reduced in said processes. Thisinvention also relates to methods for reducing plating and/or gritformation in processes for preparing an aqueous polymer emulsions usefulas thickening agents in aqueous compositions. This invention furtherrelates to polymers which are soluble in, or swelled by, an aqueousalkaline medium to provide thickeners for use in aqueous coatingcompositions, especially latex paints.

2. Background of the Invention

Processes for preparing alkali soluble aqueous polymer emulsions usefulas thickeners are known in the art. Because such alkali soluble aqueouspolymer emulsions useful as thickeners contain large amounts ofcarboxyl-functional monomer and also a monomer having surfactantcharacteristics, their production has proven to be difficult. Inparticular, during the polymerization process, some of the polymerplates out on the reactor walls and other reactor surfaces and gritparticles form in the aqueous polymer emulsion product.

While some prior art processes have addressed this problem, see, forexample, U.S. Pat. No. 4,801,671, such processes have not provensatisfactory from a commercial standpoint. It has long been desired toprovide a process for producing alkali soluble aqueous polymer emulsionsuseful as thickeners in which plating and grit formation is minimized oreliminated during the process.

DISCLOSURE OF THE INVENTION

This invention relates in part to a process for preparing an aqueouspolymer emulsion useful as a thickening agent in aqueous compositions inwhich plating and/or grit formation is reduced in said process, whichcomprises copolymerizing in aqueous emulsion:

(a) about 1-99.8 weight percent of one or more alpha,beta-monoethylenically unsaturated carboxylic acids;

(b) about 0-98.8 weight percent of one or more monoethylenicallyunsaturated monomers different from component (a);

(c) about 0.1-98.9 weight percent of one or more monoethylenicallyunsaturated macromonomers different from components (a and (b);

(d) about 0-20 weight percent or greater of one or morepolyethylenically unsaturated monomers different from components (a),(b) and (c); and

(e) one or more acrylates and/or methacrylates derived from a strongacid or a salt of a strong acid different from components (a), (b), (c)and (d) in an amount sufficient to reduce plating and/or grit formationin said process, preferably from about 0.1-25 weight percent.

This invention also relates in part to a method for reducing platingand/or grit formation in a process for preparing an aqueous polymeremulsion useful as a thickening agent in aqueous compositions, whichcomprises copolymerizing in aqueous emulsion:

(a) about 1-99.8 weight percent of one or more alpha,beta-monoethylenically unsaturated carboxylic acids;

(b) about 0-98.8 weight percent of one or more monoethylenicallyunsaturated monomers different from component (a);

(c) about 0.1-98.9 weight percent of one or more monoethylenicallyunsaturated macromonomers different from components (a) and (b);

(d) about 0-20 weight percent or greater of one or morepolyethylenically unsaturated monomers different from components (a),(b) and (c); and

(e) one or more acrylates and/or methacrylates derived from a strongacid or a salt of a strong acid different from components (a), (b), (c)and (d) in an amount sufficient to reduce plating and/or grit formationin said process, preferably from about 0.1-25 weight percent.

This invention further relates in part to polymers comprising thereaction product of:

(a) about 1-99.8, preferably about 10-70, weight percent of one or morealpha, beta-mono-ethylenically unsaturated carboxylic acids, typicallymethacrylic acid;

(b) about 0-98.8, preferably about 30-85, weight percent of one or moremonoethylenically unsaturated monomers different from component (a),typically ethyl acrylate;

(c) about 0.1-98.9, preferably about 5-60, weight percent of one or moremonoethylenically unsaturated macromonomers different from components(a) and (b);

(d) about 0-20, preferably about 0-10, weight percent or greater of oneor more polyethylenically unsaturated monomers different from components(a), (b) and (c), typically trimethylol propane triacrylate; and

(e) about 0.1-25, preferably about 0.1-2, weight percent of one or moreacrylates and/or methacrylates derived from a strong acid or a salt of astrong acid different from components (a), (b), (c) and (d), typically2-sulfoethyl methacrylate.

This invention also relates in part to an emulsion of theabove-identified polymer in water, which emulsion is useful as athickening agent in aqueous compositions. In order to obtain thethickening effect, the polymer is dissolved in the aqueous compositionto be thickened.

This invention further relates in part to an aqueous composition, andmore particularly an improved latex paint composition containing theabove-defined polymer.

This invention yet further relates in part to a process for thickeningan aqueous composition which comprises adding the above-defined polymerto an aqueous composition and dissolving the polymer in the aqueouscomposition.

DETAILED DESCRIPTION

A large proportion of one or more alpha, beta-monoethylenicallyunsaturated carboxylic acid monomers can be present in the polymers ofthis invention. Various carboxylic acid monomers can be used, such asacrylic acid, methacrylic acid, ethacrylic acid, alpha-chloroacrylicacid, crotonic acid, fumaric acid, citraconic acid, mesaconic acid,itaconic acid, maleic acid and the like including mixtures thereof.Methacrylic acid is preferred. A large proportion of carboxylic acidmonomer is essential to provide a polymeric structure which willsolubilize and provide a thickener when reacted with an alkali likesodium hydroxide.

The polymers of this invention can also contain a significant proportionof one or more monoethylenically unsaturated monomers. The preferredmonomers provide water insoluble polymers when homopolymerized and areillustrated by acrylate and methacrylate esters, such as ethyl acrylate,butyl acrylate or the corresponding methacrylate. Other monomers whichcan be used are styrene, alkyl styrenes, vinyl toluene, acrylonitrile,vinylidene chloride and the like. Nonreactive monomers are preferred,those being monomers in which the single ethylenic group is the onlygroup reactive under the conditions of polymerization. However, monomerswhich include groups reactive under baking conditions or with divalentmetal ions such as zinc oxide may be used in some situations, likehydroxyethyl acrylate.

Other illustrative monoethylenically unsaturated monomers useful in thisinvention include, for example, propyl methacrylate, isopropylmethacrylate, butyl methacrylate, n-amyl methacrylate, sec-amylmethacrylate, hexyl methacrylate, lauryl methacrylate, stearylmethacrylate, ethyl hexyl methacrylate, crotyl methacrylate, cinnamylmethacrylate, oleyl methacrylate, ricinoleyl methacrylate, hydroxy ethylmethacrylate, hydroxy propyl methacrylate, methacryonitrile, acrylamide,methacrylamide, N-alkyl acrylamides, N-aryl acrylamides, N-vinylpyrrolidone and the like including mixtures thererof.

The macromonomers useful in this invention can be represented by theformula: ##STR1## wherein: R¹ is a monovalent residue of a substitutedor unsubstituted hydrophobe compound or complex hydrophobe compound;

each R² is the same or different and is a substituted or unsubstituteddivalent hydrocarbon residue;

R³ is a substituted or unsubstituted divalent hydrocarbon residue;

R⁴, R⁵ and R⁶ are the same or different and are hydrogen or asubstituted or unsubstituted monovalent hydrocarbon residue; and

z is a value of 0 or greater.

The macromonomer compounds useful in this invention can be prepared by anumber of conventional processes. Illustrative processes are described,for example, in U.S. Pat. Nos. 4,514,552, 4,600,761, 4,569,965,4,384,096, 4,268,641, 4,138,381, 3,894,980, 3,896,161, 3,652,497,4,509,949, 4,226,754, 3,915,921, 3,940,351, 3,035,004, 4,429,097,4,421,902, 4,167,502, 4,764,554, 4,616,074, 4,464,524, 3,657,175,4,008,202, 3,190,925, 3,794,608, 4,338,239, 4,939,283 and 3,499,876. Themacromonomers can also be prepared by methods disclosed in copendingU.S. patent application Ser. No. 07/887,645, filed May 29, 1992, whichis incorporated herein by reference.

Illustrative substituted and unsubstituted divalent hydrocarbon residuesrepresented by R² in formula (I) above include those described for thesame type of substituents in formulae (i) and (ii) below. Illustrativesubstituted and unsubstituted monovalent hydrocarbon residuesrepresented by R⁴, R⁵ and R⁶ in formula (I) above include thosedescribed for the same type of substituents in formulae (i) and (ii)below.

Illustrative R³ substituents include, for example, the organic residueof ethers, esters, urethanes, amides, ureas, urethanes, anhydrides andthe like including mixtures thereof. The R³ substituent can be generallydescribed as a "linkage" between the complex hydrophobe bearingsurfactant or alcohol, and the unsaturation portion of the macromonomercompound. Preferred linkages include the following: urethane linkagesfrom the reaction of an isocyanate with a nonionic surfactant; urealinkages from the reaction of an isocyanate with an amine bearingsurfactant; unsaturated esters of surfactants such as the esterificationproduct of a surfactant with of an unsaturated carboxylic acid or anunsaturated anhydride; unsaturated esters of alcohols; esters of ethylacrylate oligomers, acrylic acid oligomers, and allyl containingoligomers; half esters of surfactants such as those made by the reactionof a surfactant with maleic anhydride; unsaturated ethers prepared byreacting vinyl benzyl chloride and a surfactant or by reacting an allylglycidyl ether with a surfactant, alcohol, or carboxylic add.

The oxyalkylene moieties included in the macromonomer compounds offormula (I) may be homopolymers or block or random copolymers ofstraight or branched alkylene oxides. Mixtures of alkylene oxides suchas ethylene oxide and propylene oxide may be employed. It is understoodthat each R² group in a particular substituent for all positive valuesof z can be the same or different.

Illustrative monovalent residues of substituted and unsubstitutedhydrophobe compounds represented by R¹ in formula (I) include, forexample, those substituted and unsubstituted monovalent hydrocarbonresidues described for the same type of substituents in formulae (i) and(ii) below.

Illustrative monovalent residues of substituted and unsubtituted complexhydrophobe compounds represented by R¹ in formula (I) include, forexample, those derived from substituted and unsubstituted complexhydrophobe compounds represented by the formula: ##STR2## wherein R₁ andR₂ are the same or different and are hydrogen or a substituted orunsubstituted monovalent hydrocarbon residue, R₃ is a substituted orunsubstituted divalent or trivalent hydrocarbon residue, each R₄ is thesame or different and is a substituted or unsubstituted divalenthydrocarbon residue, each R₅ is the same or different and is asubstituted or unsubstituted divalent hydrocarbon residue, R₆ ishydrogen, a substituted or unsubstituted monovalent hydrocarbon residueor an ionic substituent, a and b are the same or different and are avalue of 0 or 1, and x and y are the same or different and are a valueof 0 or greater; provided at least two of R₁, R₂, R₃, R₄, R₅ and R₆ area hydrocarbon residue having greater than 2 carbon atoms in the case ofR₁, R₂ and R₆ or having greater than 2 pendant carbon atoms in the caseof R₃, R₄ and R₅.

Other monovalent residues of substituted and unsubstituted complexhydrophobe compounds represented by R¹ in formula (I) include, forexample, those derived from substituted and unsubstituted complexhydrophobe compounds represented by the formula: ##STR3## wherein R₇ andR₈ are the same or different and are hydrogen or a substituted orunsubstituted monovalent hydrocarbon residue, R₁₁ and R₁₄ are the sameor different and are hydrogen, a substituted or unsubstituted monovalenthydrocarbon residue or an ionic substituent, R₉ and R₁₂ are the same ordifferent and are a substituted or unsubstituted divalent or trivalenthydrocarbon residue, each R₁₀ is the same or different and is asubstituted or unsubstituted divalent hydrocarbon residue, each R₁₃ isthe same or different and is a substituted or unsubstituted divalenthydrocarbon residue, R₁₅ is a substituted or unsubstituted divalenthydrocarbon residue, d and e are the same or different and are a valueof 0 or 1, and f and g are the same or different and are a value of 0 orgreater; provided at least two of R₇, R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₄and R₁₅ are a hydrocarbon residue having greater than 2 carbon atoms inthe case of R₇, R₈, R₁₁ and R₁₄ or having greater than 2 pendant carbonatoms in the case of R₉, R₁₀, R₁₂, R₁₃ and R₁₅.

Illustrative substituted and unsubstituted monovalent hydrocarbonresidues contain from 1 to about 50 carbon atoms or greater and areselected from alkyl radicals including linear or branched primary,secondary or tertiary alkyl radicals, such as methyl, ethyl, n-propyl,isopropyl, amyl, sec-amyl, t-amyl, 2-ethylhexyl and the like; arylradicals such as phenyl, naphthyl and the like; arylalkyl radicals suchas benzyl, phenylethyl, triphenylmethylethane and the like; alkylarylradicals such as octylphenyl, nonylphenyl, dodecylphenyl, tolyl, xylyland the like; and cycloalkyl radicals such as cyclopentyl, cyclohexyl,cyclohexylethyl and the like. The permissible hydrocarbon residues maycontain fluorine, silicon, or other non-carbon atoms.

Preferably, the substituted and unsubstituted hydrocarbon residues areselected from alkyl and aryl radicals which contain from about 1 to 30carbon atoms or greater. More preferably, the alkyl radicals containfrom 1 to 18 carbon atoms, while the aryl, arylalkyl, alkylaryl andcycloalkyl radicals preferably contain from 6 to 18 carbon atoms orgreater.

In a preferred embodiment of this invention, R₁, R₂, R₇ and R₈ canindividually be a hydrocarbon radical represented by the formula:##STR4## wherein R₁₆ and R₁₇ are as defined for R₁, R₂, R₇ and R₈ above,h and i are the same or different and are a value of 0 or 1, and R₁₈ isas defined for R₃ above. For compounds represented by formulae (i) and(ii), it is understood that each formula (iii) radical in a givencompound may be the same or different and the R₁₆ and/or R₁₇ groups maythemselves be a formula (iii) radical to provide complex hydrophobes ofa dendritic or of a cascading nature as described below. Further, R₄,R₅, R₁₀ and R₁₃ can individually be a hydrocarbon radical represented bythe formula:

    --CH[(OR.sub.19).sub.j OR.sub.20 ]--                       (iv)

wherein R₁₉ is as defined for R₄, R₅, R₁₀ and R₁₃ above, R₂₀ is asdefined for R₆, R₁₁ and R₁₄ above, and j is a value of 0 or greater.

Illustrative ionic substituents for R₆, R₁₁, R₁₄ and R₂₀ includecationic and anionic substituents such as sulfates, sulfonates,phosphates and the like. R₆, R₁₁, R₁₄ and R₂₀ may preferably be anorganic residue containing 1 or more hydroxyls or nitrogen derivativesor epoxides or other reactive groups which may or may not containunsaturation.

Other illustrative terminal groups which are described by R₆, R₁₁, R₁₄and and R₂₀ include, for example, hydrocarbon residues which may containallylic or vinylic unsaturation, acrylic or methacrylic functionality,styryl or alpha-methylstyryl functionality, and the like, such as thereaction product between the terminal alcohol (R₆, R₁₁, R₁₄ and R₂₀ =H)and glycidyl methacrylate, isocyanatoethyl methacrylate, alpha,alpha-dimethyl-m-isopropenyl benzyl isocyanate (m-TMI), and the like.Other examples of terminal groups may include hydrocarbon residues ofalkyl, aryl, aralkyl, alkaryl, and cycloalkyl radicals which may or maynot be substituted with one or more of the following: hydroxyl,carboxyl, isocyanato, amino, mono- or disubstituted amino, quaternaryammonium, sulfate, sulfonate, phosphate, epoxy, and the like and may ormay not contain other non-carbon atoms including silicon or fluorine.Also included can be divalent siloxy radicals. Other nonhydrocarbonterminal groups may include sulfates, phosphates, and the like.

Illustrative divalent hydrocarbon residues represented by R₃, R₄, R₅,R₉, R₁₀, R₁₂, R₁₃, R₁₅, R₁₈ and R₁₉ in the above formulae includesubstituted and unsubstituted radicals selected from alkylene,-alkylene-oxy-alkylene-, -arylene-oxy-arylene-, arylene, alicyclicradicals, phenylene, naphthylene, -phenylene- (CH₂)_(m) (Q)_(n)(CH₂)_(m) -phenylene- and -naphthylene- (CH₂)_(m) (Q)_(n) (CH₂)_(m)-naphthylene- radicals, wherein Q individually represents a substitutedor unsubstituted divalent bridging group selected from --CR₂₁ R₂₂ --,--O--, --S--, --NR₂₃ --, --SiR₂₄ R₂₅ -- and --CO--, wherein R₂₁ and R₂₂individually represent a radical selected from hydrogen, alkyl of 1 to12 carbon atoms, phenyl, tolyl and anisyl; R₂₃, R₂₄ and R₂₅ individuallyrepresent a radical selected from hydrogen and methyl, and each m and nindividually have a value of 0 or 1. More specific illustrative divalentradicals represented by R₃, R₄, R₅, R₉, R₁₀, R₁₂, R₁₃, R₁₅, R₁₈ and R₁₉include, e.g., 1,1-methylene, 1,2-ethylene, 1,3-propylene, 1,6-hexylene,1,8-octylene, 1,12-dodecylene, 1,4-phenylene, 1,8-napthylene,1,1'-biphenyl-2,2'-diyl, 1,1'-binaphthyl-2,2'-diyl,2,2'-binaphthyl-1,1'-diyl and the like. The alkylene radicals maycontain from 2 to 12 carbon atoms or greater, while the arylene radicalsmay contain from 6 to 18 carbon atoms or greater. Preferably, R₃, R₄,R₅, R₉, R₁₀, R₁₂, R₁₃, R₁₅, R₁₈ and R₁₉ are an alkylene or aryleneradical. The permissible divalent hydrocarbon residues may containfluorine, silicon, or other non-carbon atoms.

Illustrative trivalent hydrocarbon residues represented by R₃, R₉, R₁₂and R₁₈ in the above formulae include substituted and unsubstitutedradicals selected from <CH--, <C(R₂₆)--, <CR₂₇ -- and the like, whereinR₂₆ is a substituted or unsubstituted monovalent hydrocarbon residue asdescribed herein and R₂₇ is a substituted or unsubstituted divalenthydrocarbon residue as described herein.

Of course, it is to be further understood that the hydrocarbon residuesin the above formulae may also be substituted with any permissiblesubstituent. Illustrative substituents include radicals containing from1 to 18 carbon atoms such as alkyl, aryl, aralkyl, alkaryl andcycloalkyl radicals; alkoxy radicals; silyl radicals such as --Si(R₂₈)₃and --Si(OR₂₈)₃, amino radicals such as --N(R₂₈)₂ ; acyl radicals suchas --C(O)R₂₈ ; acyloxy radicals such as --OC(O)R₂₈ ; carbonyloxyradicals such as --COOR₂₈ ; amido radicals such as --C(O)N(R₂₈)₂ and--N(R₂₈)COR₂₈ ; sulfonyl radicals such as --SO₂ R₂₈ ; sulfinyl radicalssuch as --SO(R₂₈)₂ ; thionyl radicals such as SR₂₈ ; phosphonyl radicalssuch as --P(O)(R₂₈)₂ ; as well as halogen, nitro, cyano, trifluoromethyland hydroxy radicals and the like, wherein each R₂₈ can be a monovalenthydrocarbon radical such as alkyl, aryl, alkaryl, aralkyl and cycloalkylradicals, with the provisos that in amino substituents such as--N(R₂₈)₂, each R₂₈ taken together can also compromise a divalentbridging group that forms a heterocyclic radical with the nitrogen atom,in amido substituents such as --C(O)N(R₂₈)₂ and --N(R₂₈)COR₂₈, each R₂₈bonded to N can also be hydrogen, and in phosphonyl substituents such as--P(O)(R₂₈)₂, one R₂₈ can by hydrogen. It is to be understood that eachR₂₈ group in a particular substituent may be the same or different. Suchhydrocarbon substituent radicals could possibly in turn be substitutedwith a permissible substituent such as already herein outlined above.

Preferred alkylene oxides which can provide random or block oxyalkyleneunits in the complex hydrophobe compounds represented by formulae (i)and (ii) include alkylene oxides such as ethylene oxide, propyleneoxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,2- and 2,3-pentyleneoxide, cyclohexylene oxide, 1,2-hexylene oxide, 1,2-octylene oxide,1,2-decylene oxide, and higher alpha-olefin epoxides; epoxidized fattyalcohols such as epoxidized soybean fatty alcohols and epoxidizedlinseed fatty alcohols; aromatic epoxides such as styrene oxide and2-methylstyrene oxide; and hydroxy- and halogen-substituted alkyleneoxides such as glycidol, epichlorohydrin and epibromohydrin. Thepreferred alkylene oxides are ethylene oxide and propylene oxide. Alsoincluded can be hydrocarbon residues from substituted and unsubstitutedcyclic esters or ethers such as oxetane and tetrahydrofuran. It isunderstood that the compounds represented by formulae (i) and (ii)herein can contain random and/or block oxyalkylene units as well asmixtures of oxyalkylene units. It is further understood that each R₄,R₅, R₁₀, R₁₃ and R₁₉ group in a particular substituent for all positivevalues of x, y, f, g and j respectively can be the same or different.

The values of x, y, z, f, g and j are not narrowly critical and can varyover a wide range. For example, the values of x, y, z, f, g and j canrange from 0 to about 200 or greater, preferably from about 0 to about100 or greater, and more preferably from about 0 to about 50 or greater.Any desired amount of alkylene oxide can be employed, for example, from0 to about 90 weight percent or greater based on the weight of thecomplex hydrophobe compound.

Referring to the general fomulae (i) and (ii) above, it is appreciatedthat when R₁, R₂, R₇ and/or R₈ are a hydrocarbon residue of fomulae(iii) above, the resulting compound may include any permissible numberand combination of hydrophobic groups of the dendritic or cascadingtype. Such compounds included in the above general fomulae should beeasily ascertainable by one skilled in the art. Illustrative complexhydrophobe compounds having at least one active hydrogen useful in thisinvention and processes for preparation thereof are disclosed incopending U.S. patent application Ser. No. 07/887,648, filed May 29,1992, U.S. Pat. No. 5,488,180 which is incorporated herein by reference.

In a preferred embodiment of this invention, the structure shown informula (iii) can be a residue of the reaction product betweenepichlorohydrin and an alcohol, including those alcohols whose residuescan be described by formula (iii), or a phenolic, or a mixture thereof.The structures which result can be described as complex hydrophobes of adendritic or of a cascading nature. Pictorially, they can be describedas shown below: ##STR5##

Preferred macromonomer compounds useful in this invention include thoserepresented by the formulae: ##STR6## wherein R¹, R², R⁴, R₁₉, z and jare as defined herein.

The macromonomer compounds useful in this invention can undergo furtherreaction(s) to afford desired derivatives thereof. Such permissiblederivatization reactions can be carried out in accordance withconventional procedures known in the art. Illustrative derivatizationreactions include, for example, esterification, etherification,alkoxylation, amination, alkylation, hydrogenation, dehydrogenation,reduction, acylation, condensation, carboxylation, oxidation, silylationand the like, including permissible combinations thereof. This inventionis not intended to be limited in any manner by the permissiblederivatization reactions or permissible derivatives of macromonomercompounds.

More particularly, the hydroxyl-terminated macromonomer compounds ofthis invention can undergo any of the known reactions of hydroxyl groupsillustrative of which are reactions with acyl halides to form esters;with ammonia, a nitrile, or hydrogen cyanide to form amines; with alkylacid sulfates to form disulfates; with carboxylic adds and addanhydrides to form esters and polyesters; with alkali metals to formsalts; with ketenes to form esters; with acid anhydrides to formcarboxylic adds; with oxygen to form aldehydes and carboxylic adds;ring-opening reactions with lactones, tetrahydrofuran; dehydrogenationto form aldehydes, isocyanates to form urethanes, and the like.

The monoethylenically unsaturated macromonomer component is subject toconsiderably variation within the formula presented previously. Theessence of the macromonomer is a hydrophobe or complex hydrophobecarrying a polyethoxylate chain (which may include some polypropoxylategroups) and which is terminated with at least one hydroxy group. Whenthe hydroxy-terminated polyethoxylate hydrophobe or complex hydrophobeused herein is reacted with a monoethylenically unsaturatedmonoisocyanate, for example, the result is a monoethylenicallyunsaturated urethane in which a hydrophobe or complex hydrophobepolyethoxylate structure is associated with a copolymerizablemonoethylenic group via a urethane linkage.

The monoethylenically unsaturated compound used to provide themonoethylenically unsaturated macromonomer is subject to wide variation.Any copolymerizable unsaturation may be employed, such as acrylate andmethacrylate unsaturation. One may also use allylic unsaturation, asprovided by allyl alcohol. These, preferably in the form of ahydroxy-functional derivative, as is obtained by reacting a C₂ -C₄monoepoxide, like ethylene oxide, propylene oxide or butylene oxide,with acrylic or methacrylic acid to form an hydroxy ester, are reactedin equimolar proportions with an organic compound, such as toluenediisocyanate or isophorone diisocyanate. The preferred monoethylenicmonoisocyanates are styryl, as in alpha, alpha-dimethyl-m-isopropenylbenzyl isocyanate (m-TMI), and methacrylol isocyanate. Other suitableorganic compounds include, for example, monoethylenically unsaturatedesters, ethers, amides, ureas, art hydrides, other urethanes and thelike.

The polymers of this invention may further be modified by introducing anamount of component (d), namely, one or more polyethylenicallyunsaturated copolymerizable monomers effective for crosslinking, such asdiallylphthalate, divinylbenzene, allyl methacrylate, trimethylolpropane triacrylate, ethyleneglycol diacrylate or dimethacrylate,1,6-hexanediol diacrylate or dimethylacrylate, diallyl benzene, and thelike. Thus, from about 0.05 or less to about 20% or greater of suchpolyethylenically unsaturated compound based on total weight of monomermay be included in the composition forming the polymer. The resultingpolymers are either highly branched or in the form of three-dimensionalnetworks. In the neutralized salt form, those networks swell in anaqueous system to act as a highly efficient thickener.

Other illustrative polyethylenically unsaturated monomers useful in thisinvention include, for example, any copolymerizable compound whichcontains two or more nonconjugated points of ethylenic unsaturation ortwo or more nonconjugated vinylidene groups of the structure, CH₂ ═C═,such as divinyltoluene, trivinylbenzene, divinylnaphthalene,trimethylene glycol diacrylate or dimethacrylate,2-ethylhexane-1,3-dimethyacrylate, divinylxylene, divinylethylbenzene,divinyl ether, divinyl sulfone, allyl ethers of polyhdric compounds suchas of glycerol, pentaerythritol, sorbitol, sucrose and resorcinol,divinylketone, divinylsulfide, allyl acrylate, diallyl maleate, diallylfumarate, diallyl phthalate, diallyl succinate, diallyl carbonate,diallyl malonate, diallyl oxalate, diallyl adipate, diallyl sebacate,diallyl tartrate, diallyl silicate, triallyl tricarballylate, triallylaconitate, triallyl citrate, triallyl phosphate,N,N-methylenediacrylamide, N,N'-methylenedimethacrylamide,N,N'-ethylidenediacrylamide and1,2-di-(a-methylmethylenesulfonamide)ethylene.

The polymers of this invention also include an amount of component (e),namely one or more acrylates and/or methacrylates derived from a strongacid or a salt of a strong acid. As used herein, "strong acid(s)" shallmean those acids fully dissociated at a pH of 2 and shall include, forexample, sulfonic acid and the like. Illustrative acrylates andmethacrylates derived from a strong acid or a salt of a strong acidinclude, for example, 2-sulfoethyl methacrylate, 3-sulfopropylmethacrylate, 3-sulfopropyl acrylate, and the like. Suitable saltsinclude, for example, the sodium, potassium, ammonium, etc., salt of thestrong acid. The acrylates and methacrylates derived from a strong acidor a salt of a strong acid are employed in the emulsion polymerizationprocess in an amount sufficient to reduce plating and/or grit formationduring said process, preferably from about 0.1 to about 25 weightpercent, more preferably from about 0.1 to about 10 weight percent, andmost preferably from about 0.1 to about 2.0 weight percent.

The use of acrylates and/or methacrylates derived from a strong acid ora salt of a strong acid in a process for preparing an aqueous polymeremulsion useful as a thickening agent in aqueous compositionssignificantly reduces both waste polymer ("scrap") in the form ofreactor residue ("plating") and the formation of large particle sizesuspended aggregates ("grit") in the aqueous polymer emulsion products.Such plating and grit can jeopardize the commercial and economicviability of a process or product. This invention provides foreconomical high solids processes, and greatly enhances the mechanical,heat-age and shelf stability of latexes without adversely affecting thefilm properties of paints that contain the thickeners. While not wishingto be bound to any particular theory, it is believed that the acrylatesand/or methacrylates of strong acids or salts of strong acids provideionized or ionizable groups on the polymer particle surface making thepolymer particle more resistant to flocculation or agglomeration causedby shear forces and added ionic agents, e.g., initiators andsurfactants, and thereby reducing plating and/or grit formation. Theaqueous polymer emulsions of this invention have sufficientelectrostatic repulsive forces between the polymer particles to provideimproved mechanical stability to the emulsion and reduced reactorfouling, i.e., reduced polymer scrap.

The polymers of this invention can be prepared via a variety ofpolymerization techniques known to those skilled in the art, providedsuch polymerization techniques impart (i) colloidal stabilization to thepolymer particles and (ii) a medium wherein electrostatic interaction ofthe polymer particles can take place. The technique of polymerizationinfluences the microstructure, monomer sequence distribution in thepolymer backbone and its molecular weight to influence the performanceof the polymer. Illustrative polymerization techniques include, forexample, conventional and staged aqueous emulsion polymerization viabatch, semi-continuous, or continuous processes, miniemulsion andmicroemulsion polymerization, aqueous dispersion polymerization,interfacial polymerization, aqueous suspension polymerization, and thelike.

For purposes of this invention, the terms "aqueous emulsion", "aqueousemulsion polymerization", and like terms, are contemplated to includeall those polymerizations which provide (i) colloidal stabilization ofthe polymer particles and (ii) a medium wherein electrostaticinteraction of the polymer particles can take place. As used herein, theterm "aqueous polymer emulsions", and like terms, are contemplated toinclude all those polymer products prepared by aqueous emulsion oraqueous emulsion polymerization.

The thickeners of this invention possess structural attributes of twoentirely different types of thickeners (those which thicken by alkalisolubilization of a high molecular weight entity, and those whichthicken due to association), and this may account for the superiorthickener properties which are obtained herein.

To obtain an estimate of thickening efficiency, the product can bediluted with water to about 1% solids content and then neutralized withalkali. The usual alkali is ammonium hydroxide, but sodium and potassiumhydroxide, and even amines, like triethylamine, may be used forneutralization. The neutralized product dissolves in the water toprovide an increase in the viscosity. In the normal mode of addition,the unneutralized thickener is added to a paint and then neutralized.This facilitates handling the thickener because it has a lower viscositybefore neutralization. This procedure also makes more water availablefor the paint formulation.

The polymers of this invention are preferably produced by conventionalaqueous emulsion polymerization techniques, using appropriateemulsifiers for emulsifying the monomers and for maintaining the polymerobtained in a suitable, dispersed condition. Commonly used anionicsurfactants such as sodium lauryl sulfate, dodecylbenzene sulfonate andethoxylated fatty alcohol sulfate can be used as emulsifiers. Theemulsifier may be used in a proportion of 1/2 to 6% of the weightmonomers.

Preferably, water-soluble initiators such as alkali metal or ammoniumpersulfate are used in amounts from 0.01 to 1.0% on the weight ofmonomers. A gradual addition thermal process employed at temperaturesbetween 60° C. to 100° C. is preferred over redox systems.

The polymerization system may contain small amounts (0.01 to 5% byweight, based on monomer weight) of the chain transfer agent mercaptanssuch as hydroxyethyl mercaptan, B-mercaptopropionic acid and alkylmercaptans containing from about 4 to 22 carbon atoms, and the like. Theuse of mercaptan modifier reduces the molecular weight of the polymer.

In an embodiment of this invention, the emulsion polymerization iscarried out in the presence of one or more buffers. Illustrative buffersuseful in this invention include, for example, sodium acetate, sodiumbicarbonate, potassium carbonate and the like. The buffers are employedin the emulsion polymerization process in an amount sufficient to reduceplating and/or grit formation during said process, preferably from about0.01 to about 1.0 weight percent, more preferably from about 0.1 toabout 0.5 weight percent.

The polymer may be utilized in a variety of ways to provide thethickener or thickened compositions of this invention. For example, thepolymer, while in aqueous dispersion or dry form, may be blended into anaqueous system to be thickened followed by addition of a neutralizingagent. Alternatively, the polymer may first be neutralized in aqueousdispersion form and then blended with the aqueous system. Preferably, ifco-thickening by a surfactant is desired, the components are separatelyblended (as dry components or as dispersions or slurries) into anaqueous dispersion to be thickened, followed by the neutralization step.Although aqueous concentrates of the polymer in acid form and thesurfactant may be formed and added to an aqueous dispersion to bethickened as needed, followed by neutralization, such concentrates tendto be too viscous for easy handling. It is nevertheless possible toprepare either a dry blend or an aqueous, high solids composition whichis sufficiently low in viscosity as to be pumpable or pourable, and thento further thicken the admixture by addition of an alkaline material.

The polymer thickener may be provided in a dry state in number of ways.For example, the unneutralized polymer may be spray or drum dried and,if desired, blended with a surfactant co-thickener. However, it is alsopossible to spray dry or otherwise dehydrate the neutralized polymerthickener, and then reconstitute the aqueous thickener dispersion at afuture time and place by agitation in a aqueous medium, provided the pHof the dispersion is maintained at pH 7 or higher.

The more usual method of application of the dispersion of this inventionfor aqueous thickening is to add the aqueous dispersion of the polymerto the medium to be thickened and, after mixing, to introduce analkaline material to neutralize the acid. The major portion of thethickening effect is obtained in a few minutes upon neutralization. Inthe presence of high concentrations of electrolytes, the viscositydevelopment may take much longer. This method of applying a polymer toan aqueous system before neutralization enables one to handle a highsolids thickener in a non-viscous state, to obtain uniform blend, andthen to convert to a highly viscous condition by the simple addition ofan alkaline material to bring the pH of the system to 7 or above.

The aqueous solutions thickened with the neutralized polymers of thisinvention exhibit good viscosity stability even at a pH as high as 13.

The polymer may be used to thicken compositions under acidic conditionsin the presence of a relatively large amount of surfactants wherein thethickened composition, for example, an aqueous system, has a pH below 7,even as low as 1.

An enhancement of thickening (herein termed "co-thickening") can resultupon the addition of a surfactant to an aqueous system containing thepolymer of this invention, when the polymer is neutralized. In somecases the thickening can be enhanced up to about 40 times the viscosityafforded by the neutralized polymer alone. A wide range of surfactantsmay be used. Although trace amounts of surfactant may be residuallypresent from the polymerization of the monomers comprising the polymer(for example, whatever may remain of the about 1.5 weight percentsurfactant on monomers), such mounts of surfactant are not believed toresult in any measurable co-thickening.

On the basis of an aqueous system containing about 0.1 to 5% by weightof polymer solids, a useful amount of surfactant for optimumco-thickening is about 0.1 to 1.0% by weight of the total system. Asindicated, the amounts of polymer and surfactant cothickener may varywidely, even outside these ranges, depending on polymer and surfactanttype and other components of the aqueous system to be thickened.However, the co-thickening can reach a maximum as surfactant is addedand then decreases as more surfactant is added. Hence, it may beuneconomical to employ surfactant in amounts outside the statedconcentrations and polymer/surfactant ratios, but this can be determinedin a routine manner in each case.

The preferred method of application of the polymer and the surfactantfor aqueous thickening is to add in any sequence the polymer and thesurfactant to the medium to be thickened and, after mixing, to introducean alkaline material to neutralize the acid. This method of applyingpolymer and surfactant to an aqueous system before neutralizationenables one to handle a high solids thickener in a non-viscous state, toobtain a uniform blend, and then to convert to a highly viscouscondition by the simple addition of an alkaline material to bring the pHof the system to 7 or above. However, the polymer in the aqueous systemmay also be neutralized before addition of the surfactant.

The surfactants which may be used include nonionics and anionics, singlyor in combination, the selection necessarily depending uponcompatibility with other ingredients of the thickened or thickenabledispersions of this invention. Cationic and amphoteric surfactants mayalso be used provided they are compatible with the polymer and otheringredients of the aqueous system, or are used in such small amounts asnot to cause incompatibility.

Suitable anionic surfactants that may be used include the higher fattyalcohol sulfates such as the sodium or potassium salt of the sulfates ofalcohols having from 8 to 18 carbon atoms, alkali metal salts or aminesalts of high fatty add having 8 to 18 carbon atoms, and sulfonatedalkyl aryl compounds such as sodium dodecyl benzene sulfonate. Examplesof nonionic surfactants include alkylphenoxypolyethoxyethanols havingalkyl groups of about 7 to 18 carbon atoms and about 9 to 40 or moreoxyethylene units such as octylphenoxypolyethoxyethanols,dodecylphenoxypolyethoxyethanols; ethylene oxide derivatives oflong-chain carboxylic acids, such as lauric, myristic, palmitic, oleic;ethylene oxide condensates of long-chain alcohols such as lauryl orcetyl alcohol, and the like.

Examples of cationic surfactants include lauryl pyridinium chloride,octylbenzyltrimethylammonium chloride, dodecyltrimethylammonium chloridecondensates of primary fatty amines and ethylene oxide, and the like.

The foregoing and numerous other useful nonionic, anionic, cationic, andamphoteric surfactants are described in the literature, such asMcCutcheon's Detergents & Emulsifiers 1981 Annual, North AmericaEdition, MC Publishing Company, Glen Rock, N.J. 07452, U.S.A.,incorporated herein by reference.

In general, solvents and non-solvents (or mixtures of solvents,non-solvents, other organics and volatiles) can be used to manipulatethe viscosity of polymer containing systems. Mineral spirits can actlike a co-thickener, and the water solubility of other solvents caninfluence how much mineral spirits can be added before the solutionseparates into a two phase system. The co-thickening with mineralspirits has utility in textile printing pastes, and in waterborneautomotive basecoats. These systems usually contain mineral spirits(because of the pigments used therein), so that the mineral spiritsprovide an economical way of increasing viscosity and improving theefficiency of the thickener.

The amount of the polymer that may be dissolved in any given aqueouscomposition may fall within a wide range depending on the particularviscosity desired.

Thus, although any effective amount of the polymer may be employed fordissolution, typically from about 0.05 to about 20%, preferably fromabout 0.1 to about 5%, and most preferably from about 0.1 to about 3% byweight, based on the weight of the final aqueous composition includingpolymer is used.

For latex paint compositions, the polymer may be dissolved therein in anamount of from about 0.05 to about 5%, and preferably from about 0.1 toabout 3% by weight, based on the weight of the total compositionincluding polymer.

The polymers of this invention may be employed as thickeners forcontrolling viscosity of any aqueous based composition. An aqueous basedcomposition is an aqueous composition as herein defined to be acomposition wherein water comprises at least 10% by weight of the totalcomposition (including 100% water).

For example, aqueous dispersions, emulsions, suspensions, solutions,slurries and the like, may be thickened by the polymers of thisinvention.

Typical aqueous compositions include compositions to be applied totextiles such as latex adhesives, warp sizes, backings for rugs andother pile fabrics. The polymer may also be used when thickening isdesired in the purification of raw water such as the saline water usedin the recovery of oil from exhausted oil wells by water floodingtechniques. Other aqueous coatings compositions to which the polymer canbe added for thickening purposes include drilling muds, caulks,adhesives, coating compositions such as paper coatings, furniturefinishes, ink compositions, latex paints, foundary core washes, and thelike.

Preferably, the polymer is used to thicken aqueous coating compositions,and more preferably latex paint compositions.

Examples of suitable latex paint compositions that can be prepared bythis invention include those based on resins or binders ofacrylonitrile, copolymers of acrylonitrile wherein the comonomer is adiene like isoprene, butadiene or chloroprene, homopolymers of styrene,homopolymers and copolymers of vinyl halide resins such as vinylchloride, vinylidene chloride or vinyl esters such as vinyl acetate,vinyl acetate homopolymers and copolymers, copolymers of styrene andunsaturated acid anydrides like maleic anhydrides, homopolymers andcopolymers of acrylic and methacrylic acid and their esters andderivatives, polybutadiene, polyisoprene, butyl rubber, natural rubber,ethylene-propylene copolymers, olefins resins like polyethylene andpolypropylene, polyvinyl alcohol, carboxylated natural and syntheticlatices, reactive latexes such as those having ethylenic unsaturationconnected to the polymer through pendant flexible or dangling sidechains, epoxies, epoxy esters and similar polymeric latex materials.

Latex paint compositions are well known in the art and typicallycomprise an emulsion, dispersion or suspension of discrete particles ofresin binder and pigment in water. Optional ingedients typicaly includethickeners, antifoam agents, plasticizers, surfactants, coalescingagents, and the like. High solids latex compositions, i.e., up to about50 percent by weight solids, can be prepared in accordance with thisinvention.

The polymers described herein are useful in a variety of aqueoussystems, such as textile coatings (woven and nonwoven), latex paintformulations, cosmetic formulations, pigment dispersions and slurries,dentrifrices, hand lotions, liquid detergents, quenchants, agriculturalchemicals, concrete additives, transmission fluids, waste watertreatment (flocculants), turbulent drag reduction, aircraft anti-icing,automotive coatings (OEM and refinish), architectural coatings,industrial coatings and the like. It is understood that the aqueouspolymer emulsions of this invention can contain any permissibleconventional additives employed in conventional amounts for theparticular end-use application.

As used herein, the term "complex hydrophobe" is contemplated to includeall permissible hydrocarbon compounds having 2 or more hydrophobegroups, e.g., bis-dodecylphenyl, bis-nonylphenyl, bis-octylphenyl andthe like.

For purposes of this invention, the term "hydrocarbon" is contemplatedto include all permissible compounds having at least one hydrogen andone carbon atom. In a broad aspect, the permissible hydrocarbons includeacyclic and cyclic, branched and unbranched, carbocyclic andheterocyclic, aromatic and nonaromatic organic compounds which can besubstituted or unsubstituted.

As used herein, the term "substituted" is contemplated to include allpermissible substituents of organic compounds unless otherwiseindicated. In a broad aspect, the permissible substituents includeacyclic and cyclic, branched and unbranched, carbocyclic andheterocyclic, aromatic and nonaromatic substituents of organiccompounds. Illustrative substituents include, for example, alkyl,alkyloxy, aryl, aryloxy, hydroxy, hydroxyalkyl, amino, aminoalkyl,halogen and the like in which the number of carbons can range from 1 toabout 20 or more, preferably from 1 to about 12. The permissiblesubstituents can be one or more and the same or different forappropriate organic compounds. This invention is not intended to belimited in any manner by the permissible substituents of organiccompounds.

The invention is illustrated by certain of the following examples.

EXAMPLE 1 Preparation of 1,3-Bis(nonylphenoxy)-2-propanol

To a five neck, two liter round bottom flask equipped with an additionfunnel, thermometer, nitrogen dispersant tube, mechanical stirrer, and adecanting head with a water-cooled condenser were added 220 grams (1.00mole) of nonylphenol and 250 milliliters of cyclohexane. The solutionwas then heated to reflux and 2.8 grams (1.3 wt. % based on nonylphenol)of potassium hydroxide in 10 milliliters of water was slowly added tothe flask. After essentially all the water was recovered in thedecanting head (10 milliliters+1 milliliter formed), 250.7 grams (0.91mole) of nonylphenyl glycidyl ether as added dropwise. During theaddition of the glycidyl ether, the reaction temperature was maintainedbetween 60° and 80° C. After the addition was complete, the solution wasrefluxed for four hours. The contents of the flask were then washed witha five percent aqueous solution of phosphoric acid, and the organiclayer was separated from the water layer and washed twice with deionizedwater. The reaction mixture was then placed in a one liter round bottomflask, and the remaining cyclohexane and unreacted nonylphenol wererecovered by distillation, first at atmospheric pressure, then undervacuum at 0.2 mm Hg. The kettle temperature was not allowed to exceed180° C. during the distillation to prevent discoloration of the product.The concentrated solution was then refiltered to give 425 grams of apale-yellow liquid. End-group MW analysis gave a molecular weight of506.8 (theoretical MW=496.8). Ir and nmr spectra were identical topreviously recorded spectra for the compound.

EXAMPLE 2 Preparation of 1,3-Bis(nonylphenoxy)-2-propanol

To a five neck, two liter round bottom flask, equipped with an additionfunnel, thermometer, nitrogen dispersant tube, mechanical stirrer, and adecanting head with a water-cooled condenser, were added 300 millilitersof cyclohexane and 451.7 grams (2.05 mole) of nonylphenol. The solutionwas then heated to reflux and 58.9 grams (1.05 mole) of potassiumhydroxide in 60 milliliters of water was slowly added via the additionfunnel. After essentially all the water was recovered in the decantinghead (60 milliliters+19 milliliters formed), the reaction was cooled to40° C., and 92.5 grams (1.00 mole) of epichlorohydrin was slowly added.During the addition, the reaction temperature was maintained below 60°C. by controlling the rate of epichlorohydrin addition. After all theepichlorohydrin was added, the solution was allowed to stir for onehour, and then brought to reflux for an additional three hours. Thereaction mixture was then filtered under vacuum through a steam-jacketedBuchner funnel to remove the potassium chloride formed as a by-product.The filtration process was performed a total of three times to removethe majority of the salts. The reaction mixture was then placed in a oneliter round bottom flask, and the remaining cyclohexane and unreactednonylphenol were recovered by distillation, first at atmosphericpressure, then under vacuum at 0.2 mm Hg. The kettle temperature was notallowed to exceed 180° C. during the distillation to preventdiscoloration of the product. The concentrated solution was thenrefiltered to give 275 grams of a pale-yellow liquid. End-group MWanalysis gave a molecular weight of 459.7 (theoretical MW=496.8). Ir andnmr spectra were identical to previously recorded spectra for thecompound.

EXAMPLE 3 Preparation of 5 Mole Ethoxylate of1,3-Bis(nonylphenoxy)-2-propanol

To a 500 milliliter, stainless steel, high pressure autoclave wascharged 200 grams (0.40 mole) of 1,3-bis(nonylphenoxy)-2-propanol, whichcontained a catalytic amount of the potassium salt of the alcohol asdescribed in Example 1. After purging the reactor with nitrogen, thealcohol was heated to 130° C. with stirring, and 86.9 grams (2.0 mole)of ethylene oxide was added over a two hour period. The reactiontemperature and pressure were maintained from 130° C. to 140° C. and 60psig during the course of the reaction. After the addition of ethyleneoxide was complete, the reaction mixture was held at 140° C. for anadditional hour to allow all the ethylene oxide to cook out. Thereaction mixture was dumped while hot, under nitrogen, and neutralizedwith acetic acid to yield 285 grams of a pale-yellow liquid.

EXAMPLE 4 Preparation of Adduct of Nonylphenyl Glycidyl Ether and 5 MoleEthoxylate of 1,3-Bis(nonylphenoxy)-2-propanol

To a five neck, one liter, round bottom flask equipped as in Example 1was added 119.8 grams (0.17 mole) of the 5 mole ethoxylate of1,3-bis(nonylphenoxy)-2-propanol and 100 milliliters of cyclohexane. Themixture was refluxed (100° C.) for one hour to remove residual water,and then cooled to 50° C. under nitrogen to add 0.5 grams of BF₃ /Et₂ O.Nonylphenyl glycidyl ether (46.0 grams, 0.17 mole) was then added to theflask over a one hour period, and the reaction was heated to reflux.After three hours at reflux, the reaction mixture was transferred to aseparatory funnel, while hot, and washed with a saturated aqueoussolution of sodium bicarbonate. The organic layer was separated from thewater layer, and washed twice with hot deionized water. The washes wereperformed at 50° C. to facilitate the separation of the two layers. Thewater and cyclohexane were then evaporated from the organic layer, undervacuum, to yield 145 grams of a pale-yellow, viscous liquid. End-groupmolecular weight analysis gave a molecular weight of 880 (theoreticalmolecular weight=993).

EXAMPLE 5 Preparation of Poly(nonylphenol glycidyl ether)

To a 500 milliliter round bottom equipped with an overhead stirrer,nitrogen inlet, reflux condenser, additional funnel, and temperaturecontroller was charged 1.9 grams of ethanol (22 mmoles) and 200 grams ofcyclohexane. The solution was brought to 50° C. Once heated, 0.5milliliters (4 mmoles) of BF₃ /Et₂ O was added using a 2 millilitersyringe. Once the acid was added, 100.0 grams of nonylphenol glycidylether (362 mmoles) was added dropwise so as to maintain a reactiontemperature of 45° C.-55° C. Once the glycidyl ether was added, thesolution is refluxed for 3 hours, then cooled to about 50° C.

While hot (<60° C.) the organic was transferred to a separatory funneland was washed once with 100 milliliters of 5% sodium bicarbonatesolution. The aqueous layer was drained and the organic was washed twomore times with 100 milliliter portions of deionized water. The aqueouslayers were decanted and the organic was dried for at least 1 hour overmagnesium sulfate. Once dry the magnesium sulfate was filtered from theorganic which was stripped of solvent using a rotary evaporator. Thefinal yield of viscous polymer was 100 grams. The GPC molecular weightwas Mw=2600 and the Mn=1700 based on monodisperse polystyrene standards.

EXAMPLE 6 Ethoxylation of Poly(nonylphenol glycidyl ether)

To a 500 milliliter stainless steel Zipperclave was added 60.0 grams(0.035 moles based on an approximate molecular weight of 1700 gram/mole)of the resin prepared in Example 5 along with 0.5 grams of potassiumhydroxide. The vessel was attached to an automated ethoxylation unit andwas heated to 50° C. The vessel was continuously purged with nitrogenfor 15 minutes and was then heated to 100° C. where it was againcontinuously purged with nitrogen for another 15 minutes. The vessel wasthen heated to 140° C. and was given a series of 6 purges by pressuringthe vessel up to 80 psi, and then venting. Once the venting process wascomplete, the vessel was pressured to 20 psi with nitrogen.

The ethylene oxide lines were opened to the motor valves along with themain feed line on the Zipperclave. The feed was continued and the vesselpressure was regulated at 55 psi and a temperature of 140° C. Theautomation was designed to hold the temperature and the pressure withinsafe operating limits while addition of ethylene oxide proceeded througha pair of motor control valves. The feed was allowed to continue until60.0 grams of ethylene oxide (1.362 moles) was added based on adifference weight of the feed cylinder. After the feed was complete, thereaction was allowed to continue for 1 hour after which the vessel wascooled to 60° C., purged 4 times with nitrogen to 80 psi and was dumpedto a container. The final product yield was 115 grams with a theoreticalyield of 120 grams. The GPC molecular weight of the product was Mw=3550and the MN=2930 based on monodisperse polystyrene standards.

EXAMPLE 7 Preparation of Poly(phenyl glycidyl ether)

To a 500 milliliter round bottom equipped with an overhead stirrer,nitrogen inlet, reflux condenser, addition funnel, and temperaturecontroller was charged 47.06 grams of phenol (500 mmoles) and 100 gramsof toluene. The solution was brought to 50° C. Once heated, 1.0milliliter (8 mmoles) of BF₃ /Et₂ O was added using a 2 millilitersyringe. Once the add was added, 68.18 grams of phenyl glycidyl ether(454 mmoles) was added dropwise so as to maintain a reaction temperatureof 45° C.-55° C. Once the glycidyl ether was added, the solution isrefluxed for 3 hours, then cooled to about 50° C.

While hot (<60° C.) the organic was transferred to a separatory funneland was washed once with 100 milliliters of 5% sodium bicarbonatesolution. The aqueous layer was drained and the organic was washed twomore times with 100 milliliter portions of deionized water. The aqueouslayers were decanted and the organic was dried for at least 1 hour overmagnesium sulfate. Once dry the magnesium sulfate was filtered from theorganic which was stripped of solvent using a rotary evaporator. Thefinal yield of viscous polymer was 90.3 grams (with 11% unreactedphenol). The GPC molecular weight was Mw=470 and the Mn=310 (on averagea trimer) based on monodisperse polystyrene standards.

EXAMPLE 8 Preparation of 1,3-Bis(phenoxy)-2-propanol using the CascadingPolyol Technique

To a 1 liter round bottom flask equipped with an overhead stirrer,nitrogen inlet, reflux condenser, addition funnel, and temperaturecontroller was charged 94.11 grams of phenol (1 mole), 12.86 grams oftetraethylammonium iodide (0.05 moles), 3.00 grams of water (0.17moles), 42.08 grams of potassium hydroxide (0.75 moles), and 250 gramsof toluene. To a 100 milliliter additional funnel was charged 23.13grams of epichlorohydrin (0.25 moles) and 50 grams of toluene. Thesolution was brought to 65° C. at which time the epichlorohydrinsolution was added over a period of 15 minutes while maintaining areaction temperature of 65° C.±5° C. The reaction was allowed to proceedfor 48 hours.

After 48 hours, the solution was cooled down to room temperature. Thetoluene solution was washed with two 250 milliliters portions ofdeionized water. The aqueous layers were drained off, and the toluenewas removed along with unreacted phenol using a rotary evaporator. Thefinal yield of product was 64.5 grams which was 106% of theory (residualis phenol). Final product purity was about 95% as shown by GPC.

EXAMPLE 9 Dimerization of 1,3-Bis(phenoxy)-2-propanol using theCascading Polyol Technique

To a 250 milliliter round bottom flask equipped with an overheadstirrer, nitrogen inlet, reflux condenser, additional funnel, andtemperature controller was charged 20.03 grams of1,3-bis-(phenoxy)-2-propanol prepared in Example 8 (82 mmoles), 2.06grams of tetraethylammonium iodide (8 mmoles), 0.49 grams of water (27mmoles), 6.51 grams of potassium hydroxide (116 mmoles), and 125 gramsof toluene. To a 100 milliliter addition funnel was charged 3.61 gramsof epichlorohydrin (39 mmoles) and 25 grams of toluene. The solution wasbrought to 65° C. at which time the epichlorohydrin solution was addedover a period of 15 minutes while maintaining a reaction temperature of65° C.±5° C. The reaction was allowed to proceed for 48 hours.

After 48 hours, the solution was cooled down to room temperature. Thetoluene solution was washed with two 250 milliliter portions ofdeionized water. The aqueous layers were drained off, and the toluenewas removed using a rotary evaporator. The final yield of product was21.6 grams which was 101% of theory. GPC showed two major components ofthe product. The first was the starting material at about 41% (Mn=220)and the second was the coupled product at about 59% (Mn=520).

EXAMPLE 10 Preparation of 1,3-Bis(hexadecyloxy)-2-propanol using theCascading Polyol Technique

To a 500 milliliter round bottom flask equipped with an overheadstirrer, nitrogen inlet, reflux condenser, additional funnel, andtemperature controller was charged 60.61 grams of hexadecanol (0.25moles), 6.18 grams of tetraethylammonium iodide (0.024 moles), 1.44grams of water (0.082 moles), 20.20 grams of potassium hydroxide (0.36moles), and 125 grams of toluene. To a 100 milliliter addition funnelwas charged 11.10 grams of epichlorohydrin (0.12 moles) and 25 grams oftoluene. The solution was brought to 65° C. at which time theepichlorohydrin solution was added over a period of 15 minutes whilemaintaining a reaction temperature of 65° C.±5° C. The reaction wasallowed to proceed for 48 hours.

After 48 hours, the solution was cooled down to room temperature. Thetoluene solution was washed with two 250 milliliter portions ofdeionized water. The aqueous layers were drained off, and the toluenewas removed using a rotary evaporator. The final yield of product was70.9 grams which is 109% of theory (residual is hexadecanol).

EXAMPLE 11 Sulfation of1,3-Bis(nonylphenoxy)-2-propanol-block-(propylene oxide)₁₀-block-(ethylene oxide)₁₀

To a 250 milliliter round bottom flask equipped with an overheadstirrer, a temperature controller, and a vacuum adapter was added 75.0grams of the material from Example 13 (49 mmoles). The kettle was thenevacuated to <20 mmHg and heated to 100° C. to remove any water. After 1hour, the kettle was cooled to 60° C. while under vacuum. When reaching60° C., vacuum was broken with nitrogen and 5.3 grams of sulfamic add(54 mmoles) was added. After charging the sulfamic acid, the kettle washeated to 110° C. and evacuated to <20 mmHg. The reaction was allowed toproceed for 3 hours.

At the end of the hold period, the kettle was cooled to 85° C. andvacuum was broken with nitrogen. 1.2 grams of diethanolamine (11 mmoles)was slowly added under a blanket of nitrogen. This solution was stirredfor 30 minutes. 10 grams of ethanol was added to the kettle and thetemperature was regulated to 55° C. This solution was stirred for 30minutes. The heat was removed from the kettle and 30 grams of wateralong with 20 grams of ethanol were added while maintaining goodagitation. The solution was stirred for 15 minutes or until cooled toroom temperature (<35° C.).

The pH was checked by dissolving 2 grams of the product solution in 18grams of deionized water. If the pH was below 6.5, 0.2 gram incrementsof diethanolamine was added until the pH is between 6.5 and 7.5.

EXAMPLE 12 Preparation of1,3-Bis(nonylphenoxy)-2-propanol-block-(propylene oxide)₁₀

To a 500 milliliter stainless steel Zipperclave was added 100.0 grams(0.202 moles) of 1,3-bis(nonylphenoxy)-2-propanol prepared in Example 1along with 0.7 grams of potassium hydroxide. The vessel was attached toan automated unit and was heated to 50° C. The vessel was continuouslypurged with nitrogen for 15 minutes and was then heated to 100° C. whereit was again continuously purged with nitrogen for another 15 minutes.The vessel was then heated to 140° C. and is given a series of 6 purgesby pressuring the vessel up to 80 psi, and then venting. Once theventing process was completed, the vessel was pressured to 20 psi withnitrogen.

Lines connected to a cylinder which had been precharged with 117.0 gramsof propylene oxide (2.02 moles) were opened to the motor valves alongwith the main feed line on the Zipperclave. The feed was continued andthe vessel pressure was regulated at 55 psi and a temperature of 140° C.The automation was designed to hold the temperature and the pressurewithin safe operating limits while addition of ethylene oxide proceededthrough a pair of motor control valves. The feed was allowed to continueuntil all of the propylene oxide had been fed. After the feed wascomplete, the reaction was allowed to continue for 1 hour after whichthe vessel was cooled to 60° C., purged 4 times with nitrogen to 80 psiand was dumped to a container. The final product yield was 211 gramswith a theoretical yield of 277 grams. The GPC molecular weight of theproduct was Mw=650 and the Mn=490 based on monodisperse polystyrenestandards.

EXAMPLE 13 Preparation of1,3-Bis(nonylphenoxy)-2-propanol-block-(propylene oxide)₁₀-block-(ethylene oxide)₁₀

To a 500 milliliter stainless steel Zipperclave was added 75.0 grams ofthe propoxylate prepared in Example 12 (0.070 moles) along with 0.3grams of potassium hydroxide. The vessel was attached to an automatedethoxylation unit and was heated to 50° C. The vessel was continuouslypurged with nitrogen for 15 minutes and was then heated to 100° C. whereit was again continuously purged with nitrogen for another 15 minutes.The vessel was then heated to 140° C. and was given a series of 6 purgesby pressuring the vessel up to 80 psi, and then venting. Once theventing process was completed, the vessel was pressured to 20 psi withnitrogen.

The ethylene oxide lines were opened to the motor valves along with themain feed line on the Zipperclave. The feed was continued and the vesselpressure was regulated at 55 psi and a temperature of 140° C. Theautomation was designed to hold the temperature and the pressure withinsafe operating limits while addition of ethylene oxide proceeded througha pair of motor control valves. The feed was allowed to continue until30.7 grams ethylene oxide (0.696 moles) was added based on a differenceweight of the feed cylinder. After the feed was complete, the reactionis allowed to continue for 1 hour after which the vessel was cooled to60° C., purged 4 times with nitrogen to 80 psi and was dumped to acontainer. The final product yield was 99 grams with a theoretical yieldof 106 grams.

EXAMPLE 14 Preparation of Bis(nonylphenoxy) Adduct of 1,4-ButanediolDiglycidyl Ether

To a five neck, two liter round bottom flask equipped with an additionfunnel, thermometer, nitrogen dispersant tube, mechanical stirrer, and adecanting head with a water-cooled condenser were added 506.8 grams(2.30 mole) of nonylphenol and 350 milliliters of cyclohexane. Thesolution was heated to reflux, and 6.5 grams (1.3 weight percent basedon nonylphenol) of potassium hydroxide in 15 milliliters of water wasslowly added to the round bottom flask. After all the water wasrecovered in the decanting head (15 milliliters+2 milliliters formed),220 grams (1.09 mole) of 1,4-butanediol diglycidyl ether was addeddropwise between 60° and 80° C. After the addition was complete, thesolution was refluxed for four hours. The contents of the flask werethen washed with a five percent aqueous solution of phosphoric acid, andthe organic layer was separated from the water layer and washed twicewith deionized water. The reaction mixture was then placed in a oneliter round bottom flask, and the remaining cyclohexane and unreactednonylphenol were recovered by distillation, first at atmosphericpressure, then under vacuum at 0.2 mm Hg. The kettle temperature was notallowed to exceed 180° C. during the distillation to preventdiscoloration of the product. The concentrated solution was thenrefiltered to give 710 grams of a pale-yellow liquid. Molecular weightby end-group MW analysis was 689.9 (theoretical MW=643.0). Ir and nmrspectra were consistent with the expected structure of the product.

EXAMPLE 15 Preparation of 3 Mole Ethoxylate of1,3-Bis(nonylphenoxy)-2-propanol

To a five hundred milliliter Zipperclave reactor were charged, undernitrogen, 200.1 grams (0.43 mole) of 1,3-bis(nonylphenoxy)-2-propanolprepared in Example 2 and 0.20 grams (0.1 weight percent) of BF₃ /Et₂ O.The reaction mixture was heated to 80° C., and 55.1 grams (1.25 mole) ofethylene oxide was fed to the reactor over a two hour period. After allthe ethylene oxide was fed, the reaction mixture was allowed to cook outfor one hour and then dumped hot, under nitrogen, into a jar containing160 milliliters of a one percent aqueous solution of sodium hydroxide.The organic layer was separated from the water layer and washed twicewith deionized water. The washes were performed at 90° C. to facilitatethe separation of the two layers. The product was then dried byazeotropic removal of the water, using cyclohexane (300 milliliters) asthe entrainer. The cyclohexane was stripped off under vacuum to give apale-yellow liquid with a molecular weight by end-group MW analysis of601.7 (theoretical MW=629). Ir and nmr spectra were consistent with theexpected structure of the product.

EXAMPLE 16 Preparation of 8 Mole Ethoxylate of Bis(nonylphenoxy) Adductof 1,4-Butanediol Diglycidyl Ether

To a five hundred milliliter Zipperclave reactor were charged, undernitrogen, 150.2 grams (0.22 mole) of bis(nonylphenoxy) adduct of1,4-butanediol diglycidyl ether prepared in Example 14 and 0.30 grams(0.2 weight percent) of BF₃ /Et₂ O. The reaction mixture was heated to80° C., and 77.5 grams (1.76 mole) of ethylene oxide was fed to thereactor over a two hour period. After all the ethylene oxide was fed,the reaction mixture was allowed to cook out for one hour and thendumped hot, under nitrogen, into a jar containing 160 milliliters of aone percent aqueous solution of sodium hydroxide. The organic layer wasseparated from the water layer and washed twice with deionized water.The washes were performed at 90° C. to facilitate the separation of thetwo layers. The product was then dried by azeotropic removal of thewater, using cyclohexane (300 milliliters) as the entrainer. Thecyclohexane was stripped off under vacuum to give a pale-yellow liquidwith a molecular weight by end-group MW analysis of 1047 (theoreticalMW=995). Ir and mr spectra were consistent with the expected structureof the product.

EXAMPLES 17 to 21 Preparation of Propylene Oxide and EthyleneOxide/Propylene Oxide Copolymers of 1,3-Bis(nonylphenoxy)-2-propanol

To a 500 milliliter stainless steel autoclave was charged an amount ofpotassium hydroxide and starter listed in Table A below. The vessel washeated to 50° C. The vessel was continuously purged with nitrogen for 15minutes, and was then heated to 100° C., where it was again continuouslypurged with nitrogen for another 15 minutes. The vessel was then heatedto 140° C., and was given a series of 6 purges by pressurizing thevessel up to 80 psi, and then venting. Once the venting process wascompleted, the vessel was pressurized to 20 psi with nitrogen. The feedlines from an oxide feed cylinder (containing a charge of ethylene oxideor propylene oxide as identifed in Table A) to the autoclave wereopened. The control system fed the oxide at a rate such that the vesselpressure was regulated at 55 psi and a temperature of 140° C. Thereaction was allowed to continue for 1 hour past the end of the oxidefeed. The vessel was cooled to 60° C., purged 4 times with nitrogen to80 psi, and its contents were dumped into a tared container. The finaltheoretical and actual product yields and molecular weights determinedby gel permeation chromatography are listed in Table A.

                                      TABLE A                                     __________________________________________________________________________     ##STR7##                                                                     Product    Starter                                                            Structure  Structure                                                                           grams                                                                             grams                                                                             grams                                                                             grams                                                                             Theory                                                                            Actual    Surface                        Example                                                                            x  y  x  y  Starter                                                                           KOH PO  EO  yield                                                                             yield                                                                             Mn Mw Tension.sup.a                                                                      CMC.sup.b                 __________________________________________________________________________    17   10 40 10 0  50  0.3 0   82  132 127 2110                                                                             2340                                                                             43.3 .005                      18   10 70 10 0  50  0.3 0   145 193 188 2720                                                                             3050                                                                             47.1 .005                      19   20  0  0 0  50  0.5 117 0   167 162 1270                                                                             1530                                                                             .sup.c                                                                             .sup.c                    20   20 40 20 0  50  0.3 0   54  104 104 2280                                                                             2570                                                                             42.6 .04                       21   20 70 20 0  50  0.3 0   99  149 145 2720                                                                             3060                                                                             44.2 .03                       __________________________________________________________________________     .sup.a surface tension in dynes/cm at 1 wt. % copolymer in water              .sup.b approximate critical micelle concentration                             .sup.c water insoluble                                                   

EXAMPLES 22-33 Preparation of Poly(nonylphenyl glycidyl ether)

An amount of ethanol listed in Table B below, and 200 grams ofcyclohexane were charged to a 500 milliliter round bottom flask equippedwith an overhead stirrer, nitrogen inlet, reflux condenser, additionfunnel, and temperature controller. The solution was heated to 50° C.after which an amount of boron trifluoride etherate listed in Table Bwas added. Subsequently, 100 grams of nonylphenyl glycidyl ether wasadded dropwise to the reaction mixture so as to maintain a reactiontemperature of 45°-55° C. The solution was refluxed at 83° C. for anadditional three hours after the completion of feed, and then cooled to50° C. While hot (<60° C.), the organic material was transferred to aseparatory funnel, and was washed once with 100 milliliters of 5% sodiumbicarbonate solution. The aqueous layer was washed two more times with100 milliliter portions of deionized water. The aqueous layers weredecanted, and the organic layer was dried for at least 1 hour overmagnesium sulfate. Once dry, the magnesium sulfate was filtered from theorganic material, which was stripped of solvent using a rotaryevaporator. The molecular weights of the polymer based on gel permeationchromatography are listed in Table B.

                  TABLE B                                                         ______________________________________                                                  mL        Grams                                                     Example   BF.sub.3 /Et.sub.2 O                                                                    Ethanol     Mn   Mw                                       ______________________________________                                        22        0.5       1.9         1700 2600                                     23        1.25      10.0        410  450                                      24        0.5       5.5         470  560                                      25        1.25      5.5         870  1150                                     26        1.25      1.0         1580 2530                                     27        2.0       5.5         900  1190                                     28        2.0       1.0         1470 2310                                     29        2.0       10.0        440  500                                      30        0.5       10.0        580  730                                      31        0.5       1.0         1750 2790                                     32        0.5       1.0         1740 2640                                     33        1.6       3.32        1170 1570                                     ______________________________________                                    

EXAMPLES 34-36 Preparation of Unsymmetric Biphobes

To a 500 milliter round bottom flask equipped with an overhead stirrer,nitrogen inlet, reflux condenser, addition funnel, and temperaturecontroller was charged an amount of starting alcohol listed in Table Cbelow. The material was heated to 170° C. under nitrogen sparge, afterwhich an amount of potassium hydroxide listed in Table C was added. Anamount of epoxide listed in Table C was fed to the reaction flask usingan FMI feed pump at a rate such that addition of the epoxide wascompleted in 6 hours. Gel permeation chromatography showed that thepurity of the biphobic product was greater than 90%.

                                      TABLE C                                     __________________________________________________________________________     ##STR8##                                                                     Ex.                                                                              Alcohol                                                                            Gms Alch.                                                                           Gms KOH                                                                             Epoxide                                                                              Grams Epoxide                                                                         R1   R2                                    __________________________________________________________________________    34 nonyl-                                                                             100   2     1,2 epoxy-                                                                           108.6   nonyl-                                                                             tridecyl                                 phenol           hexadecane     phenoxy                                    35 dodecyl-                                                                           100   2     1,2 epoxy-                                                                           91.1    dodecyl-                                                                           tridecyl                                 phenol           hexadecane     phenoxy                                    36 dodecyl-                                                                            50   1     nonylphenyl                                                                          52.7    dodecyl-                                                                           nonyl-                                   phenol           glycidyl ether phenoxy                                                                            phenoxy                               __________________________________________________________________________

EXAMPLE 37 Preparation of Poly(1,2-epoxyhexadecane)

The process described in Examples 34-36 was used with 50 grams of1-hexadecanol, 1 gram of potassium hydroxide, and 49.4 grams of 1,2epoxyhexadecane. The product multiphobe had a composition of 10%hexadecanol, 55.5% biphobe (i.e., 1-hexadecoxy-2-hexadecanol), 27.7%triphobe, and 6.5% quadphobe, as determined by gel permeationchromatography.

EXAMPLE 38 Preparation of an Unsaturated Poly(nonylphenyl glycidylether)

To a 500 milliliter round bottom flask equipped with an overheadstirrer, nitrogen inlet, reflux condenser, addition funnel, andtemperature controller was charged 10 grams of allyl alcohol, 40 gramsof toluene, 0.5 grams of potassium hydroxide, and 2 grams of deionizedwater. The reaction mixture was refluxed to dryness, and cooled to 60°C. Once cool, 47.6 grams of nonylphenyl glycidyl ether was fed to thereaction vessel using a FMI pump over 35 minutes. The reaction mixturewas heated to 112° C., and refluxed for 3 hours. The solvent was removedfrom the reaction mixture by vacuum stripping. The product was cooledand recovered. The product composition was 15% allyl alcohol, 43%biphobe (e.g., 1-(2-propene-1-oxy)-3-nonylphenoxy-2-propanol) and 42%triphobe, as determined by gel permeation chromatography.

EXAMPLE 39 Solventless Macromonomer Preparation

To a 3 liter round bottom flask equipped with an overhead stirrer,nitrogen inlet and sparging tube, water cooled reflux condenser, monomeraddition tube, FMI pump and feed tank, and heating mantel andtemperature controller, 2000 grams of previously melted surfactant S-2were charged. The materials were heated to 85° C. under nitrogen spargeand mixing, and held at temperature for 1 hour to drive off residualwater. Then 0.05 grams of 4-methoxyphenol were added, and the mixturewas sparged with air for 15 minutes to activate the inhibitor. 2.4 gramsof dibutyl tin dilaurate were added, and after 15 minutes of mixing,201.25 grams of TMI were fed over 45 minutes. The mixture was held at85° C. for another 4 hours. Then 243 grams of water was pumped into thereaction mixture over a 25 minute period to wash the feed lines ofisocyanate, and to dilute the product macromonomer to 90% solids. Theproduct macromonomer was cooled and collected in a 1 gallon jug.

EXAMPLE 40 Preparation of Macromonomer Compound

Into a 1 liter round bottom reaction flask equipped with a heatingmantle, dean stark trap, condenser, thermometer, nitrogen bubbler,nitrogen purge line and stirrer was charged 300 grams of toluene and 63grams of a surfactant identified as S-1 in Table D below. With nitrogenpurge, the resulting solution was heated to reflux at approximately 110°C. and azeotroped to remove trace water to dryness. The solution wassubsequently cooled to 90° C., and 1.5 grams of bismuth hex chem 28%bismuth octoate catalyst (Mooney Chemical, Inc., Cleveland, Ohio) wascharged and allowed to mix well, after which a stoichiometric amount of95% m-TMI aliphatic isocyanate (American Cyanamid, Stamford, Conn.) wascharged. After the reaction proceeded at 90° C. for 1.3 hours, theresulting product was cooled to 70° C. and 0.03 grams of2,6-di-tert-4-methyl phenol (BHT) preservative was added. The mixturewas poured into a stainless steel pan with large surface area tofacilitate drying. The final product was a waxy material, and isdesignated herein as macromonomer M-1.

                  TABLE D                                                         ______________________________________                                         ##STR9##                                                                                                       Moles of                                    Surfactant                                                                            R.sub.1     R.sub.2 /R.sub.3                                                                            Ethoxylation                                ______________________________________                                        S-1     Nonylphenol Hydrogen (R.sub.2)                                                                          40                                          S-2     Nonylphenol Nonylphenol (R.sub.3)                                                                       40                                          S-3     Nonylphenol Nonylphenol (R.sub.3)                                                                       20                                          S-4     Nonylphenol Octylphenol (R.sub.3)                                                                       20                                          S-5     Nonylphenol Octylphenol (R.sub.3)                                                                       40                                          S-6     Nonylphenol Nonylphenol (R.sub.3)                                                                       80                                          S-7     Nonylphenol Nonylphenol (R.sub.3)                                                                       120                                         S-8     Nonylphenol Nonylphenol (R.sub.3)                                                                       20                                          S-9     Dinonylphenol                                                                             Hydrogen (R.sub.2)                                                                          50                                           S-10   Nonylphenol Hydrogen (R.sub.2)                                                                          50                                          ______________________________________                                    

EXAMPLES 41-62 Preparation of Macromonomer Compounds

In a manner similar to that described in Example 40, other macromonomerswere prepared using stoichiometric amounts of the surfactants andunsaturated compounds identified in Table E below.

                  TABLE E                                                         ______________________________________                                        Example                                                                              Surfactant                                                                              Unsaturated     Macromonomer                                 No.    Designation                                                                             Compound        Designation                                  ______________________________________                                        41     S-2       m-TMI           M-2                                          42     S-3       m-TMI           M-3                                          43     S-4       m-TMI           M-4                                          44     S-5       m-TMI           M-5                                          45     S-6       m-TMI           M-6                                          46     S-7       m-TMI           M-7                                          47     S-2       Isocyanato Ethyl                                                                              M-8                                                           Methacrylate                                                 48     S-5       Isocyanato Ethyl                                                                              M-9                                                           Methacrylate                                                 49     S-1       Methacrylic Anhydride                                                                         M-10                                         50     S-2       Methacrylic Anhdydride                                                                        M-11                                         51     S-5       Methacrylic Anhydride                                                                         M-12                                         52     S-6       Methacrylic Anhydride                                                                         M-13                                         53     S-2       Acrylic Anhydride                                                                             M-14                                         54     S-5       Acrylic Anhydride                                                                             M-15                                         55     S-6       Acrylic Anhydride                                                                             M-16                                         56     S-2       Crotonic Anhydride                                                                            M-17                                         57     S-5       Maleic Anhydride                                                                              M-18                                         58     S-8       m-TMI           M-19                                         59     S-9       m-TMI           M-20                                         60     S-10      m-TMI           M-21                                         61     S-2       Methacrylol Isocyanate                                                                        M-22                                         62     S-6       Methacrylol Isocyanate                                                                        M-23                                         ______________________________________                                    

EXAMPLE 63

Preparation of Alkali Soluble Thickener

A monomer mixture was prepared by charging 150 grams of ethyl acrylate(Aldrich), 120 grams of methacrylic acid (Aldrich), 13 grams of a 75%solution of Aerosol OT surfactant (American Cyanamid), 30 grams ofmacromonomer M-19, 3.0 grams of 2-sulfoethyl methacrylate (HampshireChemical), and 50 grams of distilled deionized water to a bottle, anddispersing the contents with vigorous shaking. To a two liter jacketedresin flask equipped with a four-bladed stainless steel mechanicalstirrer, Claisen connecting tube, Friedrichs water condenser, nitrogensparge and bubble trap, thermometer, and monomer addition inlets 872grams of water were added. Under nitrogen purge, the reaction was heatedto 80° C. by circulating temperature controlled water through thereactor jacket. 0.55 gram of sodium persulfate initiator (Aldrich) wascharged to the reactor. Five minutes later, 36 grams of the monomermixture were added to the reactor. The remainder of the monomer mixturewas charged to a one-liter graduated monomer feed cylinder. Afterallowing the initial monomer charge to react for twenty minutes to forma seed latex, the remaining monomer feed mixture was conveyed to thereaction vessel over a two hour period by FMI pumps via 1/8" Teflontubing while the reaction mixture was continuously stirred at a reactiontemperature held between 76°-82° C. The reaction was allowed to proceedfor another quarter hour, after which 0.1 gram of tert-butylhydroperoxide (Aldrich) and sodium fomaldehyde sulfoxylate (Royce) in 6grams of water were added to the latex to reduce residual monomer. Thereaction was allowed to proceed for an additional 75 minutes. Theproduct 25% solids content latex was then cooled and filtered with a 100mesh nylon cloth. The coagulum collected from the reaction vessel andfilter cloth was dried in an oven at 140° C. Table F presents the massof dried coagulum expressed as a percentage of total weight of monomerused in the reaction. The resulting latex had a pH of 3.8, had a meanparticle volume diameter of 72 nm with a polydispersity ratio of 1.06,as determined by light scattering. The mechanical stability of the latexwas determined by shearing 200 grams of the latex in a Waring® blenderfor 10 minutes, after which the latex sample was filtered with a 100mesh nylon cloth. The coagulum collected from the blender and filtercloth was dried in an oven at 140° C. Table F presents the mount ofdried coagulum expressed as a percentage of total weight of latex solidsin the test sample.

EXAMPLES 64-99 Preparation of Alkali Soluble Thickeners

In a manner similar to that described in Example 63, other alkalisoluble thickeners were prepared using the monomers identified in TablesF-K below in the amounts identified in Tables F-K. The composition ofthe monomer mixture, the solids content of the latex, and the amount anddistribution of the initiator in the process were varied. When a delayedinitiator feed was used, the initiator was dissolved in 50 grams ofwater contained in a syringe pump, and the 50 grams of water used in themonomer mixture in the process described above was omitted. The delayedcatalyst feed lasted thirty minutes longer than the period required formonomer addition. The percentage of 2-sulfoethyl methacrylate,3-sulfopropyl methacrylate and 3-sulfopropyl acrylate described inTables F-K is based on the total weight of the monomer mixture,excluding the sulfonic acid based (meth)acrylate monomer.

The sodium salt of 2-sulfoethyl methacrylate was prepared in thefollowing manner. To a beaker situated in a water and ice bath at 0° C.,72 grams of water were added, and 18 grams of 2-sulfoethyl methacrylatewere added drop-wise. After mixing and dissolution of the 2-sulfoethylmethacrylate, 8.22 grams of 0.5 normal sodium hydroxide solution wasadded drop-wise until the pH of the mixture reached 7.1. The resulting18.3% solution of the sodium salt of 2-sulfoethyl methacrylate was usedimmediately in emulsion polymeriation. The sodium and potassium salts ofother sulfuric acid based (meth)acrylate monomers were prepared in asimilar manner.

The initiator concentration (grams per 300 grams of monomer) used inpreparation of the alkali soluble thickeners in Tables F-K was asfollows (initiator initial/fed): 0.55/0 for Examples 64-67 and ControlsA and B; 0.77/0 for Examples 68-72; 0.26/0.52 for Examples 73-75;0.26/0.53 for Examples 76 and 77; 0.53/0 for Example 78; 0.77/0 forExamples 79-82 and Control C; 0.26/0.51 for Example 83 and Control D;and 0.24/0.48 for Examples 84, 86 and 87 and Control E; and 0.48/0.00for Examples 85, 88-99 and Controls F, G and H.

As used in Tables F-K below, the following abbreviations have theindicated meanings: MM=macromonomer; EA=ethyl acrylate; MAA=methacrylicacid; 2-SEM=2-sulfoethyl methacrylate; 3-SPM=3-sulfopropyl methacrylate;3-SPA=3-sulfopropyl acrylate; SSS=sodium styrene sulfonate;TDM=tert-deodecyl mercaptan; and 2-HEA=2-hydroxy ethyl acrylate.

                                      TABLE F                                     __________________________________________________________________________                 Thickener Composition by Weight                                                                       Polymer                                                                            Mechanical                          Example                                                                            Macromonomer                                                                          % MM                                                                              % MAA                                                                              % EA                                                                              % Other    Scrap %                                                                            Stability %                         __________________________________________________________________________    63   M-19    10  40   50  1% 2-SEM   0.10 7.5                                 64   M-19    10  40   50  0.5% 2-SEM 0.21 12.2                                65   M-19    10  40   60  1.5% 2-SEM 0.12 0.9                                 66   M-19    10  40   50  2.0% 2-SEM 0.06 0.7                                 67   M-19    10  40   50  1.0% 3-SPM (K salt)                                                                      0.10 --                                  68   M-19    10  40   50  1.0% 3-SPA (K salt)                                                                      0.71 --                                  69   M-19    10  40   50  1.0% 3-SPM (K salt)                                                                      0.43 --                                  70   M-19    10  40   50  1.0% 2-SEM (35%                                                                          1.13 --                                                            solids)                                             71   M-19    10  40   50  1.0% 2-SEM 0.51 --                                  72   M-19    10  40   50  1.0% 2-SEM (Na salt)                                                                     0.88 --                                  73   M-19    10  40   50  1.0% 2-SEM 0.35 0.14                                74   M-19    10  40   50  1.0% 3-SPM (K salt)                                                                      1.13 0.26                                75   M-19    10  40   50  1.0% 2-SEM (Na salt)                                                                     0.65 0.22                                76   M-19    10  40   50  1.0% 2-SEM.sup.(a)                                                                       0.05 0                                   77   M-19    10  40   50  1.0% 2-SEM.sup.(b)                                                                       0.17 0.01                                78   M-19    10  40   50  1.0% 2-SEM.sup.(c)                                                                       0.09 0.003                               A    M-19    10  40   50  None       8.67 9.74                                B    M-19    10  40   50  1.0% SSS   0.98 --                                  __________________________________________________________________________     .sup.(a) Fed 0.50 gram of sodium bicarbonate in delayed initiator stream,     .sup.(b) 0.50 gram of sodium bicarbonate in reactor charge.                   .sup.(c) 0.75 gram of sodium bicarbonate in reactor charge with one shot      initiator process.                                                       

                                      TABLE G                                     __________________________________________________________________________                 Thickener Composition by Weight                                                                      Polymer                                                                            Mechanical                           Example                                                                            Macromonomer                                                                          % MM                                                                              % MAA                                                                              % EA                                                                              % Other   Scrap %                                                                            Stability %                          __________________________________________________________________________    79   M-6     12.5                                                                              35   52.5                                                                              0.5% 2-SEM                                                                              0.31 --                                   80   M-6     12.5                                                                              35   52.5                                                                              1.0% 2-SEM                                                                              0.31 --                                   81   M-6     12.5                                                                              35   52.5                                                                              2.0% 2-SEM                                                                              0.13 0.01                                                           (K salt)                                            82   M-6     12.5                                                                              35   52.5                                                                              1.0% 2-SEM                                                                              0.08 --                                                             (K salt)                                            C    M-6     12.5                                                                              35   52.5                                                                              None      0.73 96.4                                 __________________________________________________________________________

                                      TABLE H                                     __________________________________________________________________________                 Thickener Composition by Weight                                                                         Polymer                                                                            Mechanical                        Example                                                                            Macromonomer                                                                          % MM                                                                              % MAA                                                                              % EA                                                                              % 2-HEA                                                                             % Other                                                                              Scrap %                                                                            Stability %                       __________________________________________________________________________    83   M-2     30  40   27.5                                                                              2.5   1.0% 2-SEM                                                                           0.30 --                                D    M-2     30  40   27.5                                                                              2.5   None   1.00                                   __________________________________________________________________________

                                      TABLE I                                     __________________________________________________________________________                 Thickener Composition by Weight                                                                          Polymer                                                                            Mechanical                       Example                                                                            Macromonomer                                                                          % MM                                                                              % MAA                                                                              % EA                                                                              % TDM                                                                              % Other  Scrap %                                                                            Stability %                      __________________________________________________________________________    84   M-20    30  40   30  0.3  1.0% 3-SPM                                                                             0.03 0                                                               (K salt).sup.(a)                               85   M-20    30  40   30  0.3  1.0% 3-SPM                                                                             0.05 0                                                               (K salt).sup.(b)                               86   M-20    30  40   30  0.3  1.0% 2-SEM.sup.(c)                                                                     0.06 0                                87   M-20    30  40   30  0.3  1.0% 2-SEM.sup.(d)                                                                     0.01 0                                88   M-20    30  40   30  0.3  0.25% 2-SEM.sup.(c)                                                                    0.38 12.0                             89   M-20    30  40   30  0.3  0.25% 2-SEM.sup.(d)                                                                    0.39 40.0                             90   M-20    30  40   30  0.3  0.5% 2-SEM.sup.(c)                                                                     0.46 0.22                             91   M-20    30  40   30  0.3  0.5% 2-SEM.sup.(d)                                                                     0.00 0.06                             92   M-20    30  40   30  0.3  0.5% 2-SEM.sup.(d)                                                                     0.00 0.00                                                            1.0% Sodium                                                                   Bicarbonate                                    93   M-20    30  40   30  0.3  1.0% 2-SEM.sup.(c)                                                                     0.05 0.00                             94   M-20    30  40   30  0.3  1.0% 2-SEM.sup.(c)                                                                     0.02 0.00                                                            0.25% Sodium                                                                  bicarbonate in                                                                reactor charge                                 95   M-20    30  40   30  0.3  1.0% 2-SEM.sup.(c)                                                                     0.01 0.00                                                            0.25% Sodium                                                                  bicarbonate in                                                                monomer mix                                    96   M-20    30  40   30  0.3  2.0% 2-SEM.sup.(c)                                                                     0.00 0.00                             97   M-20    30  40   30  0.3  2.0% 2-SEM.sup.(d)                                                                     0.00 0.00                             E    M-20    30  40   30  0.3  None     0.79 100                              F    M-20    30  40   30  0.3  None     0.75 100                              __________________________________________________________________________     .sup.(a) 25% total solids.                                                    .sup.(b) 43% total solids.                                                    .sup.(c) In monomer mix; 25% total solids.                                    .sup.(d) In reactor charge; 25% total solids.                            

                                      TABLE J                                     __________________________________________________________________________                 Thickener Composition by Weight                                                                       Polymer                                                                            Mechanical                          Example                                                                            Macromonomer                                                                          % MM                                                                              % MAA                                                                              % EA                                                                              % Other    Scrap %                                                                            Stability %                         __________________________________________________________________________    98   M-20    30  40   30  1.0% 3-SPM (K salt)                                                                      0.06 0                                   G    M-20    30  40   30  None       1.59 --                                  __________________________________________________________________________

                                      TABLE K                                     __________________________________________________________________________                 Thickener Composition by Weight                                                                        Polymer                                                                            Mechanical                         Example                                                                            Macromonomer                                                                          % MM                                                                              % MAA                                                                              % EA                                                                              % TDM                                                                              % Other                                                                              Scrap %                                                                            Stability %                        __________________________________________________________________________    99   M-21    15  35   50  0.2  1.0% 3-SPM                                                                           0.01 0                                  H    M-21    15  35   50  0.2  None   0.44 --                                 __________________________________________________________________________

Although the invention has been illustrated by certain of the precedingexamples, it is not to be construed as being limited thereby; butrather, the invention encompasses the generic area as hereinbeforedisclosed. Various modifications and embodiments can be made withoutdeparting from the spirit and scope thereof.

We claim:
 1. An aqueous polymer emulsion useful as a thickening agent inaqueous compositions when the polymer is dissolved therein, whichcomprises water and emulsified polymer particles prepared from monomerscomprising:(a) about 1-99.8 weight percent of one or more alpha,beta-monoethylenically unsaturated carboxylic acids; (b) about 0-98.8weight percent of one or more monoethylenically unsaturated monomersdifferent from component (a); (c) about 0.1-98.9 weight percent of oneor more monoethylenically unsaturated macromonomers different fromcomponents (a) and (b); (d) about 0-20 weight percent or greater of oneor more polyethylenically unsaturated monomers different from components(a), (b) and (c); and (e) about 0.1-25 weight percent of one or moreacrylates and/or methacrylates derived from a strong acid or a salt of astrong add different from components (a), (b), (c) and (d), said strongacid comprising an acid fully dissociated at a pH of
 2. 2. The aqueouspolymer emulsion of claim 1 wherein the polymer is a polymer preparedfrom about 10-70 weight percent of one or more alpha,beta-monoethylenically unsaturated carboxylic adds, about 30-85 weightpercent of one or more ethylenically unsaturated monomers, about 5-60weight percent of one or more monoethylenically unsaturatedmacromonomers, and about 0.1-2.0 weight percent of one or more acrylatesand/or methacrylates derived from a strong add or a salt of a strongacid, said strong acid comprising an acid dissociated at a pH of
 2. 3. Aprocess of thickening an aqueous system comprising adding to the systema polymer comprising the reaction product of:(a) about 1-99.8 weightpercent of one or more alpha, beta-monoethylenically unsaturatedcarboxylic acids; (b) about 0-98.8 weight percent of one or moremonoethylenically unsaturated monomers different from component (a); (c)about 0.1-98.9 weight percent of one or more monoethylenicallyunsaturated macromonomers different from components (a) and (b); (d)about 0-20 weight percent or greater of one or more polyethylenicallyunsaturated monomers different from components (a), (b) and (c); and (e)about 0.1-25 weight percent of one or more acrylates and/ormethacrylates derived from a strong acid or a salt of a strong aciddifferent from components (a), (b), (c) and (d);and at least partiallyneutralizing said polymer.
 4. The process of claim 3 wherein the systemis thickened further by the addition of an effective amount ofsurfactant, solvent or non-solvent.